EP0004974A2 - Process for producing a single crystal of KTiOPO4 or its analogues - Google Patents
Process for producing a single crystal of KTiOPO4 or its analogues Download PDFInfo
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- EP0004974A2 EP0004974A2 EP79101186A EP79101186A EP0004974A2 EP 0004974 A2 EP0004974 A2 EP 0004974A2 EP 79101186 A EP79101186 A EP 79101186A EP 79101186 A EP79101186 A EP 79101186A EP 0004974 A2 EP0004974 A2 EP 0004974A2
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
Definitions
- This invention relates to a process for producing large, optically useful single crystals of KTiOPO 4 and its analogues.
- Figures 1-7 show respectively the regions of the ternary phase diagrams of K 2 O/P 2 O 5 /(TiO 2 ) 2 , Rb 2 O/P 2 O 5 /(TiO 2 ) 2 , Tl 2 O/P 2 O 5 /(TiO 2 ) 2 , K 2 O/As 2 O 5 /(TiO 2 ) 2 , Rb 2 O/As 2 O 5 /(TiO 2 ) 2 , Tl 2 O/As 2 O 5 /(TiO 2 ) 2 , and RbKO/P 2 O 5 / (T 1 O 2 ) 2 within which the Pna2 1 -type MTiOXO 4 composition of this invention is the only solid phase in equilibrium with the flux.
- the invention is a method for producing a single crystal of MTiOXO 4 , of optical quality and of sufficient size for use in nonlinear optical devices, where M is at least one of K, Rb or Tl and X is at least one of P or As, by heating starting materials comprising MTiOX0 4 or its precursors with a flux M/X/O or its precursors, wherein the ratio of the starting materials or their precursors lies within the region of the ternary phase diagram M 2 O/X 2 O 5 /(TiO 2 ) 2 where the product MTiOXO 4 is the only stable solid phase in equilibrium with the flux when molten, which comprises a process selected from the group consisting of
- the proportion of the starting materials is such that there is always an excess of solid MTiOX0 4 present in the hot zone, i.e. the ratio of MTiOXO 4 to flux is greater than the saturation value. Typically this ratio ranges from about 0.25 to 20 or more, depending upon the temperature of the hot zone.
- the ratio of MTiOXO 4 to flux is less than the saturation value. Generally this ratio ranges from about 0.25 to 10, depending upon the highest temperature reached and the composition of the mixture at which complete solution occurs.
- the cooling is conducted at a rate no greater than 5°C per hour until the materials solidify, generally at about 600-800°C, and then quenching to room temperature and recovering crystals of MTiOXO 4 .
- the M/X/O flux comprises the oxides M 2 0 and X 2 O 5 or precursors such as carbonates or nitrates of M or ammonium salts of X which give rise to the oxides during the heating process.
- the flux can be made from mixtures of MH 2 XO 4 and M 2 XHO 4 and use of selected quantities allows adjustment of the M/X ratio so that the starting quantities of the ingredients fall within the proper region of the ternary phase diagram.
- Other materials which can be used as part of the flux include MHCO 3 , M 2 CO 3 , MNO 3 , NH 4 H 2 XO 4 , (NH 4 ) 2 HX0 4 and the like.
- TiO 2 can also be used as a starting material and in this case MTiOXO 4 is formed during the course of the heating.
- the amounts of M and X present must be large enough not only to combine with the Ti0 2 to form MTiOXO 4 , but also to provide the M/X/0 flux.
- the invention is carried out by placing the ingredients in a container made of platinum or another noble metal which is stable at the temperatures used and then subjecting the container and its contents to heating.
- portions of the flux are somewhat volatile; this can be controlled by growing the crystals in a closed container.
- the general procedure used to find this region of the phase diagram was to prepare various stoichiometries in the M 2 O/X 2 O 5 /(TiO 2 ) 2 ternary. This was accomplished by preparing mixtures of various combinations of Ti0 2 , MH 2 XO 3 , M 2 CO 3 , X 2 O 5 , MHCO 3 , and/or NH 4 H 2 XO 4 which were equivalent to particular composition on the ternary phase diagram. These mixtures were held at 800°C for at least 12 hours to insure equilibration and then air quenched. The water soluble flux was removed by washing the resultant material with hot water.
- Figure 1 shows the K 2 O/P 2 O 5 /(TiO 2 ) 2 ternary phase diagram at 800°C.
- KTiOPO 4 is the only solid phase in equilibrium with the flux.
- the mol fractions of each phase at points A, B, and C are:
- the line BC represents the solubility of KTiOPO 4 in the flux. This line is sensitive to changes in temperature. As the temperature is increased, line BC will move toward the center of the phase diagram, i.e. toward the KTiOPO 4 composition which is represented by point A. , At 1150°C KTiOPO 4 itself melts and the triangular single phase region ABC does not exist.
- KTiOPO 4 is only one of the solid phases present in these compositions.
- FIG. 2 shows the Rb 2 O/P 2 O 5 /(TiO 2 ) 2 ternary phase diagram at 800°C.
- RbTiOPO 4 is the only solid phase in equilibrium with the flux and is represented by point D.
- the corresponding mol fractions at each point are:
- FIG. 3 shows the Tl 2 O/P 2 O 5 /(TiO 2 ) 2 ternary phase diagram at 800°C.
- TlTiOPO 4 is the only solid phase in equilibrium with the flux and is represented by point G.
- the mol fractions at each point are:
- Figure 4 shows the K 2 O/As 2 O 5 /(TiO 2 ) 2 ternary phase diagram.
- KTiOAsO 4 is the only solid phase in equilibrium with the flux, and is represented by point J.
- the mol fractions at each point are:
- Figure 5 shows the Rb 2 O/As 2 O 5 /(TiO 2 ) 2 ternary phase diagram.
- RbTiOAsO 4 is the only solid phase in equilibrium with the flux and is represented by point M.
- the mol fractions at each point are: .
- FIG. 6 shows the Tl 2 O/As 2 O 5 /(TiO 2 ) 2 ternary phase diagram. Inside the triangular region PQR, TlTiOAsO 4 is the only solid phase in equilibrium with the flux and is represented by point P. The mol fractions at each point are:
- FIG. 7 shows the RbKO/P205/(Ti02)2 ternary phase diagram.
- (K, Rb)TiOPO 4 with the Pna2 1 structure is the only solid phase in equilibrium with the flux and is represented by point S.
- the mol fractions at each point are:
- the preferred method for making single crystals comprises mixing a combination of starting ingredients corresponding to a composition within the appropriate region of the phase diagram (e.g., for KTiOPO 4 , in the region ABC of Figure 1), placing these ingredients into a platinum container, establishing a temperature gradient in the container which may be either vertical or horizontal with the hot zone at temperatures of about 800°C to about 1000°C and with the cold zone about 10 to about 135°C cooler. This temperature gradient is maintained for about 3 days to about 3 weeks followed by cooling of the container and removing the contents, washing the material at the cold zone region in hot water to dissolve away the flux, and recovering crystals of MTiOXO 4 . It is sometimes advantageous to use acidified hot water to facilitate the dissolving of the flux.
- M and X are each comprised of only one of the stated elements.
- crystals which have mixtures of elements for M and/or X can also be grown by this process.
- the tube was heated to 1050°C, held 60 hours to homogenize the fluid system, and then cooled at a rate of 5°C/hr to 600°C. Following an air-quench the platinum tube was stripped from the solidified rod. Hot water acidified with H 3 PO 4 was used to dissolve away the flux. Crystals of KTiOPO 4 having dimensions up to 3x2x2 mm were recovered.
- a mixture of 2.40 g of powdered Ti0 2 , 9.84 g of KH 2 FO 4 and 3.55 of K 2 HFO 4 were thoroughly mixed and prefused to drive off H 2 0 and form KTiOPO 4 .
- This mixture is equivalent to a mixture of 5.94 g of KTiOFO 4 and 8.20 g of flux in which the ratio K/P is 1.325..
- the product was added to a 25 cc platinum crucible, heated for about 15 hrs at 900-1000°C, then heated at 1100°C for two hrs to further homogenize the solution, transferred to a second furnace and slow cooled from 950°C to 685°C at a rate of 2°C/hr.
- the crucible was then air quenched.
- the contents of the crucible were removed and hot water was used to dissolve the flux. Recovered were 3.65 g of clear KTiOPO 4 crystals having dimensions up to 3 x 2 x 2 mm.
- a mixture of 1.60 g of TiO 2 , 22.84 g of KH 2 AsO 4 and 3.0 g of KHCO 3 was placed in a 25 ml platinum crucible and heated to 1050°C for about 15 hrs to give a clear solution.
- the temperature was lowered and the melt cooled from 960° to 756°C at a rate of 5°C/hr.
- the crucible was then fast cooled to 575°C, air quenched, and the contents removed.
- the flux was dissolved in hot water and 2.85 g of faint yellow crystals of KTiOAsO 4 measuring up to 3 x 2 x 2 mm in size were recovered.
- the container was heated to 800°C to melt the flux and a temperature gradient of 880°C-747°C was then established. After 6-3/4 days, the container was furnace cooled to room temperature and the,contents washed with hot water to dissolve the flux. 2.22 g of untransported KTiOPO 4 were recovered from the hot zone end and 7.19 g of KTiOPO 4 crystals of optical quality and up to 5 x 4 x 4 mm in size were recovered from the cold zone end.
- a platinum crucible 1-1/2 in. (3.8 cm) in diameter and about 5 in. (7.7 cm) long was placed in a vertical furnace and arranged so that a temperature gradient could be established between the upper and lower ends of the crucible.
- the crucible was charged with a 416 gm mixture of KH 2 PO 4 and K 2 HPO 4 flux having a K/P ratio of 1.5 and 248 gm of KTiOPO 4 , i.e. 0.80 gm KTiOP04 per gm flux.
- the saturation temperature for such a mixture is 930°C. At temperatures below 930°C, there is excess KTiOP0 4 present.
- a seed crystal of KTiOP0 4 was suspended above the melt and the top of the crucible was maintained at a temperature of 912°C and the bottom at 925°C for about 15 hours. The seed was then lowered into the upper (cooler) part of the melt and kept there for about 147 hours while the top of the crucible was maintained at 906-909°C and the bottom at 922-924°C. The seed was then slowly pulled through the melt, i.e. raised, at a rate of about 0.4 mm per day.
- Crystals of RbTiOPO 4 , TlTiOPO 4 , TlTiOASO 4 , RbTiOAsO 4 and (K,Rb)TiOP0 4 can be made by using the appropriate ratio of starting ingredients so as to be within the desired triangular regions shown in Figures 2, 3, 5, 6 and 7, respectively, and using the preparative methods of Examples 1 or 5.
- the process of this invention is useful industrially for the preparation of single crystals of MTiOXO 4 of optical quality and of sufficient size for use, inter alia, as the nonlinear crystal element in nonlinear optical devices such as parametric amplifiers, oscillators and second harmonic generators.
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Abstract
Description
- This invention relates to a process for producing large, optically useful single crystals of KTiOPO4 and its analogues.
- The use of single crystals of MTiOXO4, wherein M is at least one of K, Rb, or Tl and X is at least one of P or As, in nonlinear optical devices is disclosed in U.S. Patent 3,949,323. For most optical applications, optical-quality crystals with dimensions of the order of one millimeter or more are needed. The reference patent discloses preparation of such crystals by hydrothermal methods.
- R. Masse and J. C. Grenier, Bull, Soc. Mineral Crystallogr. 94, 437-439 (1971) have reported on the preparation of powders of KTiOP04 (and the analogues RbTiOPO4 and TlTiOPO4) by heating KPO3 and T102 at temperatures between 900°C and 1200°C and then cooling at a rate of about 80°C per hour. Excess KPO3 was removed by washing with water. The ratio of KP03/Ti02 was varied over the range from 4 to 1.0 and two phases, KTiOPO4 and KTi2(PO4)3, were always found in the product.
- Crystal structure determination of KTiOPO4 crystal prepared by the flux method of Masse et al. above is disclosed by I. Tordjman et al., Zeit. fur Krist. 139, 103-115 (1974).
- The Gmelin Handbuch, Vol. 41 Ti, 8th edition (1951), reports that L. Ouvard (Comptes rendus 111, 177-179 (1890)) formed KTiO(PO4) by melting hydrated TiO2 with K4P207 and K3PO4.
- Figures 1-7 show respectively the regions of the ternary phase diagrams of K2O/P2O5/(TiO2)2, Rb2O/P2O5/(TiO2)2, Tl2O/P2O5/(TiO2)2, K2O/As2O5/(TiO2)2, Rb2O/As2O5/(TiO2)2, Tl2O/As2O5/(TiO2)2, and RbKO/P2O5/ (T1O2)2 within which the Pna21-type MTiOXO4 composition of this invention is the only solid phase in equilibrium with the flux.
- The invention is a method for producing a single crystal of MTiOXO4, of optical quality and of sufficient size for use in nonlinear optical devices, where M is at least one of K, Rb or Tl and X is at least one of P or As, by heating starting materials comprising MTiOX04 or its precursors with a flux M/X/O or its precursors, wherein the ratio of the starting materials or their precursors lies within the region of the ternary phase diagram M2O/X2O5/(TiO2)2 where the product MTiOXO4 is the only stable solid phase in equilibrium with the flux when molten, which comprises a process selected from the group consisting of
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- A(l) heating the starting materials, in proportions that there is also an excess of solid MTiOX04 relative to the M/X/0 flux at the highest temperature reached, in a temperature gradient with the hot zone at a temperature range of about 800°C to about 1000°C and the cold zone at a temperature range which is about 10°C to about 135°C cooler than the hot zone, to produce a melt,
- (2) maintaining the temperature gradient for about 3 days to about 3 weeks to allow crystal growth, and
- (3) cooling and recovering a single crystal of MTiOXO4; and
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- B(l) uniformly heating the starting materials, in proportions that there is also an excess of M/X/0 flux relative to MTiOXO4 at the highest temperature reached, to a temperature range of about 700°C to about 1100°C until a clear solution is obtained,
- (2) slowly cooling at a rate no greater than 5°C per hour to cause crystallization of MTiOXO4 and recovering same.
- In the preferred gradient heating process A, the proportion of the starting materials is such that there is always an excess of solid MTiOX04 present in the hot zone, i.e. the ratio of MTiOXO4 to flux is greater than the saturation value. Typically this ratio ranges from about 0.25 to 20 or more, depending upon the temperature of the hot zone.
- In the uniform heating process B the reverse is true, i.e. at the highest temperature reached the ratio of MTiOXO4 to flux is less than the saturation value. Generally this ratio ranges from about 0.25 to 10, depending upon the highest temperature reached and the composition of the mixture at which complete solution occurs. In this process the cooling is conducted at a rate no greater than 5°C per hour until the materials solidify, generally at about 600-800°C, and then quenching to room temperature and recovering crystals of MTiOXO4.
- The M/X/O flux comprises the oxides M20 and X2O5 or precursors such as carbonates or nitrates of M or ammonium salts of X which give rise to the oxides during the heating process. The flux can be made from mixtures of MH2XO4 and M2XHO4 and use of selected quantities allows adjustment of the M/X ratio so that the starting quantities of the ingredients fall within the proper region of the ternary phase diagram. Other materials which can be used as part of the flux include MHCO3, M2CO3, MNO3, NH4H2XO4, (NH4)2HX04 and the like.
- TiO2 can also be used as a starting material and in this case MTiOXO4 is formed during the course of the heating. When operating in this way, the amounts of M and X present must be large enough not only to combine with the Ti02 to form MTiOXO4, but also to provide the M/X/0 flux.
- The invention is carried out by placing the ingredients in a container made of platinum or another noble metal which is stable at the temperatures used and then subjecting the container and its contents to heating.
- In the temperature gradient process A, greater ccntrol of the crystal growth is obtained by inserting into the cold zone region a suitably held small crystal of MTiOX4 upon which crystal growth occurs. This is preferable to allowing spontaneous nucleation to occur at the container wall.
- With the Tl compositions above about 800°C and the K compositions above about 1050°C, portions of the flux are somewhat volatile; this can be controlled by growing the crystals in a closed container.
- Growth of large, optically useful crystals of MTiOXO4, wherein M is at least one of K, Rb, or Tl and X is at least one of P or As, from molten nonaqueous fluxes provides advantages over the hydrothermal process used previously. The invention is a more economical, low pressure process requiring less sophisticated equipment and resulting in larger production rates. It is necessary to start out with a ratio of ingredients that fall within the region of the ternary phase diagram M2O/X2O5/(TiO2)2 in which the desired product MTiOXO4 is the only stable solid phase and is in equilibrium with the molten flux. The general procedure used to find this region of the phase diagram was to prepare various stoichiometries in the M2O/X2O5/(TiO2)2 ternary. This was accomplished by preparing mixtures of various combinations of Ti02, MH2XO3, M2CO3, X2O5, MHCO3, and/or NH4H2XO4 which were equivalent to particular composition on the ternary phase diagram. These mixtures were held at 800°C for at least 12 hours to insure equilibration and then air quenched. The water soluble flux was removed by washing the resultant material with hot water. X-ray powder patterns were then used to determine the solid phase or phases which had been in equilibrium with the flux at 800°C. The region of the phase diagram which corresponds to only the one phase, MTiOXO4, in equilibrium with the flux at 800°C is thus identified. At temperatures other than 800°C, some variation in this stability region is expected; however, these variations will be primarily in the respective solubilities and the region found'at 800°C serves as a guide for the ratio of ingredients to be used at somewhat higher or lower temperatures.
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- The line BC represents the solubility of KTiOPO4 in the flux. This line is sensitive to changes in temperature. As the temperature is increased, line BC will move toward the center of the phase diagram, i.e. toward the KTiOPO4 composition which is represented by point A. , At 1150°C KTiOPO4 itself melts and the triangular single phase region ABC does not exist.
- Also shown iri Fig. 1 are the regions explored by Masse et al. and Ouvard discussed above who used TiO2 with various amounts of KPO3 and K4P2O7 and K3PO4 respectively. KTiOPO4 is only one of the solid phases present in these compositions.
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- The preferred method for making single crystals comprises mixing a combination of starting ingredients corresponding to a composition within the appropriate region of the phase diagram (e.g., for KTiOPO4, in the region ABC of Figure 1), placing these ingredients into a platinum container, establishing a temperature gradient in the container which may be either vertical or horizontal with the hot zone at temperatures of about 800°C to about 1000°C and with the cold zone about 10 to about 135°C cooler. This temperature gradient is maintained for about 3 days to about 3 weeks followed by cooling of the container and removing the contents, washing the material at the cold zone region in hot water to dissolve away the flux, and recovering crystals of MTiOXO4. It is sometimes advantageous to use acidified hot water to facilitate the dissolving of the flux.
- For many optical applications superior crystal properties will result when M and X are each comprised of only one of the stated elements. However, crystals which have mixtures of elements for M and/or X can also be grown by this process.
- The following examples are intended to illustrate the process of this invention but not to limit the scope of the invention.
- A mixture of 10 g of powdered KTiOP04 and 10 g of K6P4O13 flux, in which the K/P ratio is 1.5, prepared by heating together equimolar quantities of KH2P04 and K2HP04, was sealed into a 1/2" (1.27 cm) diam x 7" (17.78 cm) long vertical platinum tube under vacuum. The tube was heated to 1050°C, held 60 hours to homogenize the fluid system, and then cooled at a rate of 5°C/hr to 600°C. Following an air-quench the platinum tube was stripped from the solidified rod. Hot water acidified with H3PO4 was used to dissolve away the flux. Crystals of KTiOPO4 having dimensions up to 3x2x2 mm were recovered.
- A mixture of 2.40 g of powdered Ti02, 9.84 g of KH2FO4 and 3.55 of K2HFO4 were thoroughly mixed and prefused to drive off H20 and form KTiOPO4. This mixture is equivalent to a mixture of 5.94 g of KTiOFO4 and 8.20 g of flux in which the ratio K/P is 1.325.. The product was added to a 25 cc platinum crucible, heated for about 15 hrs at 900-1000°C, then heated at 1100°C for two hrs to further homogenize the solution, transferred to a second furnace and slow cooled from 950°C to 685°C at a rate of 2°C/hr. The crucible was then air quenched. The contents of the crucible were removed and hot water was used to dissolve the flux. Recovered were 3.65 g of clear KTiOPO4 crystals having dimensions up to 3 x 2 x 2 mm.
- A mixture of 1.60 g of TiO2, 22.84 g of KH2AsO4 and 3.0 g of KHCO3 was placed in a 25 ml platinum crucible and heated to 1050°C for about 15 hrs to give a clear solution. This mixture is equivalent to 4.84 g of KTiOAsO4 in 17.64 g of flux (K/As = 1.3). The temperature was lowered and the melt cooled from 960° to 756°C at a rate of 5°C/hr. The crucible was then fast cooled to 575°C, air quenched, and the contents removed. The flux was dissolved in hot water and 2.85 g of faint yellow crystals of KTiOAsO4 measuring up to 3 x 2 x 2 mm in size were recovered.
- A mixture of 6.48 g of Ti02, 37.0 g of KH2FO4, and 33.25 g of K2HPO4 was placed in a 6" long, 40 cc volume platinum container. This mixture is equivalent to a mixture of 16.0 g of KTiCP04 in 54 g of flux HFP = 1.5). After heating to 1000° and cooling, a glass was present in the container. For this mixture the saturation temperature is about 600-650°C. Then 10.8 g of KTiOPO4 crystals were placed on top of the glass material in the designated hot zone end. The total charge was equivalent to 0.5 g of KTiOPO4 per g of flux. The container was heated to 800°C to melt the flux and a temperature gradient of 880°C-747°C was then established. After 6-3/4 days, the container was furnace cooled to room temperature and the,contents washed with hot water to dissolve the flux. 2.22 g of untransported KTiOPO4 were recovered from the hot zone end and 7.19 g of KTiOPO4 crystals of optical quality and up to 5 x 4 x 4 mm in size were recovered from the cold zone end.
- A platinum crucible 1-1/2 in. (3.8 cm) in diameter and about 5 in. (7.7 cm) long was placed in a vertical furnace and arranged so that a temperature gradient could be established between the upper and lower ends of the crucible. The crucible was charged with a 416 gm mixture of KH2PO4 and K2HPO4 flux having a K/P ratio of 1.5 and 248 gm of KTiOPO4, i.e. 0.80 gm KTiOP04 per gm flux. The saturation temperature for such a mixture is 930°C. At temperatures below 930°C, there is excess KTiOP04 present. A seed crystal of KTiOP04 was suspended above the melt and the top of the crucible was maintained at a temperature of 912°C and the bottom at 925°C for about 15 hours. The seed was then lowered into the upper (cooler) part of the melt and kept there for about 147 hours while the top of the crucible was maintained at 906-909°C and the bottom at 922-924°C. The seed was then slowly pulled through the melt, i.e. raised, at a rate of about 0.4 mm per day. Pulling continued for 5 days during which time the bottom of the crucible was maintained at 924-925°C and the top at 908-910°C, At the end of the 5th day of pulling, the seed was completely removed from the melt and the furnace allowed to cool for about 20 hours before removing the seed from the furnace. A cluster of large flat crystals of KTiOPO4 had grown on the seed. Flux was then washed out of the cluster of crystals using an ultrasonic water bath. The total weight of the cluster was 9.8 gm. The largest of the optically clear crystals had dimensions of approximately 15 mm x 8 mm x 2 mm.
- Crystals of RbTiOPO4, TlTiOPO4, TlTiOASO4, RbTiOAsO4 and (K,Rb)TiOP04 can be made by using the appropriate ratio of starting ingredients so as to be within the desired triangular regions shown in Figures 2, 3, 5, 6 and 7, respectively, and using the preparative methods of Examples 1 or 5.
- From the foregoing examples, it can be seen that industrially useful, high quality, large crystals are best prepared by the method of Example 5. Industrial Applicability
- The process of this invention is useful industrially for the preparation of single crystals of MTiOXO4 of optical quality and of sufficient size for use, inter alia, as the nonlinear crystal element in nonlinear optical devices such as parametric amplifiers, oscillators and second harmonic generators.
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US898444 | 1978-04-20 | ||
US05/898,444 US4231838A (en) | 1978-04-20 | 1978-04-20 | Method for flux growth of KTiOPO4 and its analogues |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0004974A2 true EP0004974A2 (en) | 1979-10-31 |
EP0004974A3 EP0004974A3 (en) | 1979-11-14 |
EP0004974B1 EP0004974B1 (en) | 1981-08-26 |
Family
ID=25409466
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP79101186A Expired EP0004974B1 (en) | 1978-04-20 | 1979-04-19 | Process for producing a single crystal of ktiopo4 or its analogues |
Country Status (4)
Country | Link |
---|---|
US (1) | US4231838A (en) |
EP (1) | EP0004974B1 (en) |
JP (1) | JPS54145398A (en) |
DE (1) | DE2960678D1 (en) |
Cited By (11)
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EP0031223A1 (en) * | 1979-12-14 | 1981-07-01 | Monsanto Company | Crystalline calcium sodium or lithium phosphate having an asbestos-like form, a process for its preparation and composites of organic polymeric material containing it |
US4305778A (en) * | 1979-06-18 | 1981-12-15 | E. I. Du Pont De Nemours And Company | Hydrothermal process for growing a single crystal with an aqueous mineralizer |
EP0031222B1 (en) * | 1979-12-14 | 1984-03-21 | Monsanto Company | Acicular, crystalline calcium metaphosphate, a method for its production, and composites of organic polymeric material containing it |
FR2585345A1 (en) * | 1985-07-26 | 1987-01-30 | Centre Nat Rech Scient | METHOD OF FLOW SYNTHESIS OF KTIOPO4-LIKE CRYSTALS OF POTASSIUM AND TITANYL MONOPHOSPHATE |
EP0252537A1 (en) * | 1986-05-30 | 1988-01-13 | Koninklijke Philips Electronics N.V. | Process for crystal growth of KTiOPO4 from solution |
US4740265A (en) * | 1987-01-08 | 1988-04-26 | E. I. Du Pont De Nemours And Company | Process for producing an optical waveguide and the product therefrom |
FR2609976A2 (en) * | 1985-07-26 | 1988-07-29 | Centre Nat Rech Scient | Flux syntheses of crystals and epitaxies of solid isotypic KTiOPO4 solutions |
US4766954A (en) * | 1987-01-08 | 1988-08-30 | E. I. Du Pont De Nemours And Company | Process for producing an optical waveguide |
EP0410581A1 (en) * | 1989-07-28 | 1991-01-30 | Sumitomo Metal Mining Company Limited | Process for preparing single crystal of potassium titanium arsonate |
FR2660644A1 (en) * | 1990-04-06 | 1991-10-11 | Centre Nat Rech Scient | NOVEL COMPOUND OF THE K-NB-SI-O SYSTEM AND ITS DERIVATIVES, PROCESS FOR THEIR SYNTHESIS AND THEIR APPLICATIONS IN PARTICULAR IN OPTICS. |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3949323A (en) * | 1974-03-14 | 1976-04-06 | E. I. Du Pont De Nemours & Company | Crystals of (K, Rb, NH4)TiO(P, As)O4 and their use in electrooptic devices |
-
1978
- 1978-04-20 US US05/898,444 patent/US4231838A/en not_active Expired - Lifetime
-
1979
- 1979-04-18 JP JP4678379A patent/JPS54145398A/en active Granted
- 1979-04-19 EP EP79101186A patent/EP0004974B1/en not_active Expired
- 1979-04-19 DE DE7979101186T patent/DE2960678D1/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3949323A (en) * | 1974-03-14 | 1976-04-06 | E. I. Du Pont De Nemours & Company | Crystals of (K, Rb, NH4)TiO(P, As)O4 and their use in electrooptic devices |
Non-Patent Citations (1)
Title |
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GMELINS HANDBUCH DER ANORGANISCHEN CHEMIE, vol. 41, TITAN, 1951, Verlag Chemie, Weinheim, page 405 * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4305778A (en) * | 1979-06-18 | 1981-12-15 | E. I. Du Pont De Nemours And Company | Hydrothermal process for growing a single crystal with an aqueous mineralizer |
EP0031222B1 (en) * | 1979-12-14 | 1984-03-21 | Monsanto Company | Acicular, crystalline calcium metaphosphate, a method for its production, and composites of organic polymeric material containing it |
EP0031223A1 (en) * | 1979-12-14 | 1981-07-01 | Monsanto Company | Crystalline calcium sodium or lithium phosphate having an asbestos-like form, a process for its preparation and composites of organic polymeric material containing it |
FR2609976A2 (en) * | 1985-07-26 | 1988-07-29 | Centre Nat Rech Scient | Flux syntheses of crystals and epitaxies of solid isotypic KTiOPO4 solutions |
FR2585345A1 (en) * | 1985-07-26 | 1987-01-30 | Centre Nat Rech Scient | METHOD OF FLOW SYNTHESIS OF KTIOPO4-LIKE CRYSTALS OF POTASSIUM AND TITANYL MONOPHOSPHATE |
EP0215691A1 (en) * | 1985-07-26 | 1987-03-25 | Centre National De La Recherche Scientifique (Cnrs) | Process for the flux synthesis of crystals of the KTiOP04 type or monophosphate of potassium and titanyl |
EP0252537A1 (en) * | 1986-05-30 | 1988-01-13 | Koninklijke Philips Electronics N.V. | Process for crystal growth of KTiOPO4 from solution |
US4740265A (en) * | 1987-01-08 | 1988-04-26 | E. I. Du Pont De Nemours And Company | Process for producing an optical waveguide and the product therefrom |
US4766954A (en) * | 1987-01-08 | 1988-08-30 | E. I. Du Pont De Nemours And Company | Process for producing an optical waveguide |
DE3801862A1 (en) * | 1987-01-23 | 1988-08-04 | Centre Nat Rech Scient | METHOD FOR MELTING SOLUTION SYNTHESIS OF CRYSTALS AND EPITACTIC LAYERS FROM SOLID SOLUTIONS OF KTIOPO (ARROW DOWN) 4 (ARROW DOWN) ISOTYPES |
EP0410581A1 (en) * | 1989-07-28 | 1991-01-30 | Sumitomo Metal Mining Company Limited | Process for preparing single crystal of potassium titanium arsonate |
FR2660644A1 (en) * | 1990-04-06 | 1991-10-11 | Centre Nat Rech Scient | NOVEL COMPOUND OF THE K-NB-SI-O SYSTEM AND ITS DERIVATIVES, PROCESS FOR THEIR SYNTHESIS AND THEIR APPLICATIONS IN PARTICULAR IN OPTICS. |
WO1991015426A1 (en) * | 1990-04-06 | 1991-10-17 | Centre National De La Recherche Scientifique | NEW COMPOUND OF THE K-Nb-Si-O SYSTEM AND ITS DERIVATIVES, PROCESS FOR SYNTHESISING THEM AND THEIR APPLICATIONS, IN PARTICULAR IN OPTICS |
CN104178814A (en) * | 2014-08-28 | 2014-12-03 | 中国有色桂林矿产地质研究院有限公司 | Method for growing large-size rubidium titanyl phosphate monocrystalline by using hydrothermal method |
Also Published As
Publication number | Publication date |
---|---|
EP0004974A3 (en) | 1979-11-14 |
US4231838A (en) | 1980-11-04 |
DE2960678D1 (en) | 1981-11-19 |
JPH0152359B2 (en) | 1989-11-08 |
JPS54145398A (en) | 1979-11-13 |
EP0004974B1 (en) | 1981-08-26 |
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